Phthalocyanine dyestuffs



F 6 Claims. or: 260-3145) The present invention relates to new phthalocyanine dyestuffs and to a process for preparing them; more particularly it relates to dyestuffs of the general Formula 1 in which Me represents a metal atom, in particular a copper or nickel atom, Pc represents phthalocyanine, Y represents one of the groupings NH-, -SO NH- loweralkylene-NH-,

Nil-

SOaH

NIT-- --CH2-NH SOaH X represents one of the groupings -CO--, fi50 and -CO-NH-,

R represents a hydrogen atom or a lower alkylene group,

Z represents a CH=CH or CH CH -halgengroup,

R represents a hydrogen atom or a halogen atom,

11 represents a whole number from 1 to 3,

m represents a number from 0 to 2, and

p represents 1 or 2.

We have found that new valuable phthalocyanine dyestuifs of the Formula 1 can be obtained, by reacting at United States Patent 0 temperatures in the range of about 0 to about 40 C., 1 mol of the dyestuif of the general Formula 2 a R, Mc Pc l in which Pc, Me, R, Y, n, m and p are defined as above, with about 1 to 2 mols of a compound of the general Formula 3 in which A represents one of the SO -halogen, and as above.

The acylable amino groups of the starting dyestuffs of the general Formula 2 may be linked with an aromatic nucleus of the dyestutf molecule either directly or via an alkylene group, for example, a methylene, ethylene, propylene, isopropylene or 'butylene group; the alkylene group itself may be linked over a bridging member with the respective aromatic nucleus of the dyestutf molecule.

The reaction of the water-soluble starting dyestuffs of the general Formula 2 with the acid halides or isocyanates of the general Formula 3 is preferably carried out in water. The acid chlorides or isocyanates may be used either in concentrated form, if desired or required for a better distribution in the aqueous phase with preceding, simultaneous or subsequent addition of a substance having emulsifying action or a surfactant or dissolved in an organic solvent. Solvents which are suitable for this purpose are, for example, acetone, chloroform, benzene, toluene or chlorobenzene.

The reaction of the starting dyestuffs with the isocyanate compounds is carried out in the neutral or weakly alkaline pH range, if desired or required in the presence of buffer groupings -CO-halogen, N=C=O, and R and Z are defined salt mixtures.

When the condensation reaction is complete, the watersoluble dyestuffs are precipitated, if desired after previous neutralization, from the solutions or suspensions, filtered, washed and dried.

The dyestuifs obtainable by the process of the present invention may also be prepared by reacting the starting dystutfs, particularly those which are sparingly watersoluble, with the acid halides or isocyanates of the Formula 3 in an inert organic solvent. If desired or necessary, these reactions are carried out in the presence of or While adding acid-binding agents. Solvents which are suitable for this purpose are, for example, benzene, toluene, chlorobenzene, nitrobenzene, tetrahydrofurane, acetone, dimethylforrnamide or dimethylacetamide.

The acid halides or isocyanate compounds of the Formula 3, used in accordance with the present invention for preparing the drystuffs, constitute novel compounds.

The acid halides of the Formula 4 or 5 can be prepared, for example,

(a) By reacting aminobenzenecarboxylic acids or -sulfonic acids with acylating agents which introduce the radical of the vinylsulfonic acid, for example, with carbyl sulfate or vinylsulfonic acid chloride, or

(b) By allowing, for example, acetic acid anhydride, methanesulfonic acid chloride or p-toluenesulfonic acid chloride to act on isethionylaminobenzene-carboxylic acids or -sulfonic acids, whereby the hydroxyl group in e-position is esterified.

The benzene-carboxylic acidor benzenesulfonic acid derivatives obtained by the methods described under (a) and (b) may be alkylated, if desired, at the nitrogen atom bound to an aromatic nucleus, with an alkylating agent such as dimethyl sulfate or diethyl sulfate and then converted in known manner into the corresponding carboxylic acid or sulfonic acid halides.

The sulfonic acid chlorides of the Formula 3 may also be prepared from aniline derivatives of the general Formula 4 in which R and Z are defined as above, by diazotizing these compounds and subsequently reacting the diazonium salts thus obtained with sulfur dioxide in the presence of acetic acid and copper chloride according to a process described by H. Meerwein (B. 90, 841, 1957).

The isocyanate compounds of the general Formula 3 can be prepared by reacting in known manner the aniline derivatives of the general Formula 4 with phosgene, :hereby an isocyanate group is formed from the amino group.

As examples of such starting compounds, which are prepared in the manner described above and may be used in accordance with the process of the present invention, there may be mentioned the following compounds: Z-(N- methyl fl chloroethylsulfonylamino) benzene l carboxylic acid chloride, 2-( S-chloroethylsulfonylamino)- benzene-l-carboxylic acid chloride, 4-(N-methyl-B-chloroethylsulfonylamino -benZene-lcarboxylic acid chloride, 3-(N methyl-B-chloroethylsulfonylamino) benzene-lcarboxylic acid chloride, 2-(N-ethyl-fi-chloroethylsulfonylamino)-benzene-1-carboxy1ic acid chloride, 4-(N-butyli3-chloroethylsulfonylamino) benzene-l-carboxylic acid chloride, 4-(N methylvinylsulfonylamino) benzene-1- carboxylic acid chloride or -sulfonic acid chloride, 3-(N- methyl-vinylsulfonylamino)-benzene-l-sulfonic acid chloride, 4-(N-methyl-fi-chloroethylsulfonylarnino)-3-chlorobenzene-l-carboxylic acid chloride, 4-[3-chloroethylsulfonylamino-benzene-l-carboxylic acid chloride, 4-(N- methyl vinylsulfonylamino -2,5-dimethylbenzenel-isocyanate, 4-(N methyl-B-chloroethylsulfonylamino)-benzene 1 isocyanate, 3-(N-methylvinyl-sulfonylamino)- bcnzene-l-isocyanate, 4 (N-methyl-fl-chloroethylsulfonylamino)-3-methoxybenzene-l-isocyanate, 4 (N-methylfi-chloroethylsulfonylamino)-3-methoxy 2 methyibenzene-l-isocyanate, 3-(N-methyl 13 chloroethyl-sulfonylamino)-4-chlorobenzene-l-isocyanate and 4-(N-methylfi-bromoethylsulfonylamino) benzene-l-carboxyiic acid bromide.

The dyestuffs used in and obtainable by the process of the present invention may contain in addition to sulfonic acid groups and sulfonic acid amide groups further substituents in the dyestuff molecule, for example, halogen atoms.

Depending on the nature and number of the substituents present, the dyestuffs obtained are, sparingly soluble or easily soluble in water.

The dyestuffs obtained by the process of the present invention are suitable for the dyeing or printing of various natural, regenerated or synthetic fibrous materials such as cotton, viscose, regenerated cellulose, wool, silk, leather, polyamides, polyacrylonitrile, cellulose acetate or aromatic polyester fibers, depending on the nature of the dyestuffs. For these purposes, the dyestuffs of the invention may be used according to the dyeing and printing methods conventionally used in the industry, as illustrated hereinafter.

The use of the dyestuffs obtained by the process of the present invention depends in the first instance on the fibrous material to be dyed and on the constitution of the dyestuff to be employed, in particular on the number and nature of the groups present which impart solubility in water. For example, those of the novel dyestuffs which preferably contain more than one group imparting solubility in water, for example, two or more sulfonic acid and/or carboxylic acid groups in the molecule, are especially suitable for the dyeing of cellulose-containing materials, particularly of cotton.

The fixation of the novel dyestuffs on the cellulosecont-aining fibrous materials dyed according to the usual dyeing or printing methods is carried out by a treatment with an acid-binding agent, for example, sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium bicarbonate, sodium silicate, sodium triphosphate or sodium trichloroacetate and, if desired, by the action of heat. The treatment with the acid-binding agent can be carried out prior to, during or after the application of the dyestuff.

Thus, for example, cellulose-containing textile materials can be dyed according to the so-called direct dyeing method by treating the textile materials with an aqueous solution of the dyestuff in the presence of acid-binding agents, at a temperature in the range of, for example, 40 and 100 C.

For preparing dyeings, one may also apply the dyestuff to the cellulose-containing textile material by the usual dyeing and padding methods and then introduce the goods dyed into an aqueous solution of the acid-binding agent at a temperature in the range of 20 and 100 C.

Furthermore, the novel dyestuffs may be applied, for example, by padding or from a dyebath, at a temperature ranging from 20 to 100 C., to the textile material impregnated with .an aqueous solution of the acid-binding agent, and heating, if desired, after intermediate drying.

Furthermore, the textile material may be treated with an aqueous solution of the dyestuff in the presence of the acid-binding agent, squeezed and then allowed to remain at room temperature or heated for a short period, for example, by steaming, if desired, after an intermediate drying.

The aqueous dyestuff solutions used for preparing the dyeings may be combined with other substances; thus, there may be added especially electrolytes such as sodium chloride or sodium sulfate, urea, dispersing agents, surfactants and thickeners, for example, sodium alginate.

The novel dyestuffs are also suitable for the preparation of prints on cellulose materials. For this purpose, the fabric is printed with a printing paste containing the acid-binding agent and subjected to a short heat treatment, if desired, after intermediate drying. It is also possible to apply a printing paste containing one or several of the dyestuffs obtained by the process of the invention to the cellulose fabric impregnated with an acidbinding agent and to subsequently heat the printed fabric, for example, by steaming. Furthermore, the cellulose material may first be printedwith a printing paste containing one or several dyestuffs, and then treated with the aqueous solution of an acid-binding agent, preferably in the presence of electrolytes such as sodium chloride or sodium sulfate, at a temperature in the range from about 60 to 100 C. The printing pastes used for preparing the prints may also contain further substances, for example, urea, thickeners, water-in-oil emulsions, surfactants and m-nitro-benzenesulfonic acid sodium. Generally, the dyeings and prints on cellulose prepared with the novel dyestuffs are rinsed with water after the dyeing or printing process, soaped and rinsed again with water before drying.

For the dyeing of textile materials the dyestuffs of the invention, which contain no groups imparting solubility in water such, for example, as sulfonic acid, carboxylic acid or sulfonic acid amide groups, are expediently used in the form of aqueous dispersions. Such dispersions can be obtained in the usual manner, for example, by grinding the dyestuffs of the invention with a dispersing agent in water.

Finally, the novel dyestuffs may also be used for the dyeing of nitrogen-containing textile materials, for example, wool and polyamide fibers. The dyeing is car- 6 ried out from weakly alkaline, neutral or acid dyebaths which dyes cotton or regenerated cellulose turquoise blue, in the presence of compounds conventionally used in lightand wash-fast shades.

the dyeing of nitr-ogemoontaining textile materials, for example, sodium sulfate, ammonium acetate, surfactants such as quaternary ammonium salts, and non-ionic dis- 5 60 parts by weight of copper phthalocyanine are con persing agents. If desired, the pH-value of the dyebath verted into the copper phthalocyanine-tetrasulfonic acid Example 2 may be varied during the dyeing process by adding alkachloride according to the method described in Example lies or alkaline salts or by adding acids or acid salts, for 1. After having washed the product with ice-cold water, example, in such a manner as to start the dyeing at a the wet filter residue is introduced into a mixture of pH-value of 4 and to increase the pH-value during the 10 200 parts by weight of ice and 200 parts by weight of dyeing to 7.5. water and neutralized with a dilute sodium hydroxide The novel dyestulfs give in general full and clear shades solution at 0 C. to this suspension, there are added a which are distinguished by good properties of fastness, neutralized solution of 38.0 parts by weight of 1,4-diespecially by good to very good fastness to light and to amino-benzene-4-sulfonic acid in 510 parts by volume of wet processing. water and, subsequently, 37 parts by weight of sodium The following examples illustrate the invention, but carbonate and the whole is stirred for 24 hours at 30 they are not intended to limit it thereto: to 35 C. and then for 2 hours at 60 to 65 C. The

reaction product is salted out with sodium chloride, filtered off and washed with a sodium chloride solution.

The wet filter residue is dissolved in 1780 parts by volume of water and to this solution, there are added,

A mixture of 60 parts by weight of copper phthalocyin the course of one half hour, at 0 to 5 C., a solution anine and 250 parts by weight of chlorosulfonic acid is of 50 parts by weight of 3-(N-methyl-,B-chlorethylheated with stirring to 130-135 C. and kept for 11 hours sulfonylamino)-benzene-1-carboxylic acid chloride in 110 at this temperature. The mixture is then cooled to 50 parts by volume of dioxane and, simultaneously, a dilute Example 1 to 60 C.; 110 parts by weight of thionyl chloride are aqueous sodium carbonate solution in such a manner that allowed to run-in the course of 1 hour. The mixture is the pH-value is maintained at 6.5 to 7.0. When the then stirred for 4 hours at 85 to 90 C., cooled and reaction is complete, the product is salted out with introduced, with stirring, into a mixture of ice and potassium chloride, filtered off, washed with a potassium water. The precipitated copper phthalocyanine-tetra- Chl rid IHti H and dri d at 50 t0 60 C. under sulfochloride is filtered oil and washed with ice-cold water. reduced pressure. The new dyestuff which has the The wet filter residue is introduced into a mixture of formula SOaH 2 250 parts by weight of ice and 200 parts by weight of constitutes a blue powder which gives lightand washwater and neutralized at 0 C. with a dilute sodium fast greenish blue prints on cotton, when applied in the hydroxide solution. To the suspension thus obtained, presence of sodium carbonate.

there are added a neutralized solution of 38.0 parts by weight of l,3-diaminobenzene-4-sulfonic acid in 480 1 parts by volume of water and, subsequently, 37 parts by 60 pints by welgnt of copper phtpalocyamne P- weight of sodium carbonate and the whole is stirred 1; mto the.copper phthalocyamne'tfttmslilfomc acid for 24 hours at to and for 2 hours at chloride according to the method described in Example to The reaction product is Salted out with sodium 1. The sulfonic acid chloride obtained is then reacted chloride, filtered off and washed with a solution of sodium as Indicated with 1ddiamino'benzene'll'slilfcnic acid chloride The wet filter residue of the condensatlon product is dissolved in 1600 parts by volume of water. Into the The Wet filter resldue 1S dlssoived 1500 parts by solution, which, if required, has been adjusted to a pH- volume of water and then combined, in the course of value of 7 by means of Sodium carbonate there M one hour, at 0 to 5 C., with a solution of 45 parts by e troduced dropwise, in the course of 30 minutes, while weight of 4-(N-methyl-B-chlorethylsulfonylam1no)benstirring vigorously, at 0 t 5 C 50 parts by weight zene-l-carboxylic acid chloride in 100 parts by volume of 3 (N-methyl-vinyl-sulfonyl-amino)-benzene-1-isocy- Example 3 o acetone simulttfneollslyi with a dilute aqueous anate, dissolved in 150 parts by volume of acetone. The sodulm Carb nate SOIHUOH III a manner Such a the mixture is stirred for 6 hours and then potassium chloride flwalue is kept at 6.2 to 6.6. When the reaction is is added. The precipitated dyestuff is filtered 01f, Washed complete, the product is salted out with potassium chlowith an aqueous potassium chloride solution and dried. ride, filtered oil and washed with a dilute aqueous po- When this product which has the formula NI-I-C o NI-I I (HOgSh-{OuPC} SOzNHSOaH i\ 1soi cn=om CH3 2 tassium chloride solution. After drying, there is obis applied to cotton by first impregnating the cotton with tained a blue dyestulf which has the formula a solution of the dyestuff and then after-treating it with aqueous sodium hydroxide, greenish-blue dyeings are obtained which are fast to washing.

Example 4 The process is carried out as described in Example 1, but using 59.0 parts by Weight of nickel phthalocyanine instead of copper phthalocyanine.

When the dyestufi thus obtained which has the formula is applied to cotton in the presence of sodium bicarbonate, greenish-blue dyeings that have good fastness to washing, are obtained.

Example 5 57.7 parts by weight of copper phthalocyanine are converted into the copper phthalocyanine-tetrasulfonic acid chloride in the usual manner and condensed in an aqueous medium with parts by weight of l-amino-4-acetylaminobenzene or 14 parts by weight of 4-amino-formylanilide. In order to saponify the acylamino group, the whole is boiled with dilute sulfuric acid. The compound obtained which has the formula 8 is separated by means of sodium chloride, filtered off and dried at 60 C. In the presence of acid-binding agents, the new dyestufi dyes cotton greenish blue shades which are fast to light and to washing.

Example 6 60 parts by weight of copper phthalocyanine are converted as described in Example 1 into the copper phthalocyanine-tetrasulfonic acid chloride and then condensed at 20 C. with 27.6 parts by weight of 4,4-diamino-diphenyl- 3-sulfonic acid, in water and in the presence of sodium carbonate. The unreacted sulfonic acid chloride groups are subsequently saponified in a sodium alkaline medium at 60 C. The dyestuff that has formed is separated by means of sodium chloride and isolated. The compound obtained is dissolved in 2800 parts by volume of water and combined in the course of 3 hours, while stirring a vigorously, at 0 to 5 C., with a solution of 38 parts by weight of 4-(N-methyl-,8-chloroethylsulfonylamino)-benzene-l-carboxylic acid chloride in 60 parts by volume of acetone. By the simultaneous addition of an aqueous sodium carbonate solution having a strength of 10% by weight, the pH-value is kept at 6 to 7.2. When the mentioned acid chloride is consumed, the new dyestuff of the formula.

is salted out with sodium chloride, filtered off and dried at C. under reduced pressure. .A dark powder is obtained which dyes cellulose fibers in the presence of acidbinding agents intensely bluish green shades that have good fastness to washing. Dyestuffs that have similar properties can be prepared by reacting under corresponding reaction conditions the phthalocyanine dyestuffs (I) listed in the following table with the respective acid 50 chlorides or isocyanates (II).

I II Tint, on cotton Phthalocyanine dyestuil Acylating agent 1 C u? c 4-(N-methylvinyl-sulfon ylaniino)-beuzene-1-sulionic G recnish acid chloride. blue.

s o ;NH-NH1 (S 03H) 3 7/ 2 CuPc 4-(N-ethyl-B-chl0roethylsulionylamino)-benzene-1- Do.

carboxylic acid chloride.

s o :-NH-NH2 I II Tint on cotton Phthalocyanine dyestuff Acylating agent 7 3 CuPc 4-(N-butyl-B-cliloroethylsulfonylamino)-benzone-L Do.

k carhoxylic acid chloride.

S O gNH- -NH2 4 I CuPc 3-(N-methyl fi-chlorocthylsulfonylamino)-bcnzenc-1- D0.

carboxylic acid chloride.

s Oa -NH-C-Nflz (S 0 H; f 5 I CuPo 4-(N-rnethyl-vinyl-sulfonylamino)-benzene-1- D0.

k carboxylic acid chloride.

s OzNH-NH 6 CuPc |S0311 do Do.

- O2NI'I -S: NH2

a )z 7 0 111 c N H-NI-Ig 4-(N-methyl-fi-chloroethylsulfonylamino) -benzene-1- Do.

l carboxylic acid chloride.

(s02NH- son1 7 8 C uP c 4-(N-mcthyl-vinyl-sulfonylumino)-bcnzene-1-isocyanate Do.

S Oz-N NH 9 CuPc 4-(fl-chlorocthyl-sull'onylamino)-benzene-1- carboxylic D0.

acid chloride.

(CHzNI-IQ-S 03H 7 10 CuPc 4-(N-ethyLfl-cliloroethylsulionylamino)-benzene-1- 0.

carboxylic acid chloride.

3 )2 11 I Oulci do Do.

(S O ENI ICH CHQNH Example 7 98.5 parts by weight of the the formula phthalocyanine dyestutf of sequent saponification of the acetylarnino group, are suspended in 2500 parts by volume of Water and dissolved by neutralization with a binormal sodium hydroxide solution. The solution thus obtained is cooled to 0 to 5 C. and combined in the course of 2 hours, While stirring vigorously, with a solution of 35 parts by weight of 4-(N- methyl [3 chloroethyl sulfonylamino) benzene-Learboxylic acid chloride in parts by volume of acetone. By simultaneously dropwise adding a binormal sodium carbonate solution, the mixtureis kept at a pH-value of 6.5 to 7.0. The mixture is then stirred for 12 hours at 0 to 5 C. and then for 3 hours at 30 to 35 C., while mediately suspended in 1500 parts by volume of ice-water and neutralized with a dilute sodium hydroxide solution. Sodium carbonate is then introduced portionwise, while stirring vigorously, in such a manner that the pH-value is kept at 6.7 to 7.7. Instead of sodium carbonate, there may also be used other acid-binding agents such as potassium hydroxide, ammonium carbonate or ammonia. When using ammonium a part of the sulfochloride groups is converted into sulfonic acid amide groups. In this case, there is formed a condensation product which contains sulfonic acid and sulfonic acid amide groups. After 18 hours, the ,mixture is heated to to C., while I II Tint on t Phthalocyanine dyestufi Acylating agent co ton 1 H 038 S 03H 4-(N-methyl-B-chloroethylsulfonylamin o)-benzene-1- Greenish l I carboxylic acid chloride. blue.

CuPc--(S Or -NHQ-NHD, 4 l

HzN-O 2S 2 H035 d0 Do.

/CuPc+(S oz-Nrr@-s o in), l HgN-O 28 NH} 3 HOaS 2 do Do.

NiPc(S O NH-S 0 H); 4 HaN-O 2S 4 (HOQSM d0 Do.

CuIc;JSOz-NH-CH2-CH;-NHg

HzN-O 2S Example 8 parts by weight of copper phthalocyanine are converted into the copper phthalocyanine-tetrasulfonic acid chloride according to the method described in Example 1. The sulfochloride obtained is further condensed as a wet paste with the intermediate product described below.

27.6 parts by weight of 1,3-diaminobenzene-4-sulfonic acid are dissolved in 392 parts by volume of water with the addition of dilute sodium hydroxide solution so that a neutral solution is obtained. To this solution, there is added at 0 to 5 C., in the course of 3 hours, while stirring vigorously, a solution of 64.8 parts by weight of 4 (N methyl ,8 chloroethylsulfonylamino) benzenel-carboxylic acid chloride in parts by volume of acetone. The hydrochloric acid formed during the condensation is neutralized by adding a dilute sodium carbonate solution in such a manner that the pH-value is maintained at 6.0 to 6.5. As soon as the condensation is complete, the condensation product, which has partly precipitated, is completely salted out by the addition of sodium chloride, filtered off and washed with a 20% sodium chloride solution.

The washed paste and the copper phthalocyanine sulfochloride paste obtained according to paragraph 1 are im- CHz gives greenish blue dyeings on cotton which are very fast to light and to washing.

When using the same quantity by weight of 1,4-diaminobenzene-Z-sulfonic acid instead of l,3-diaminobenzene-4-sulfonic acid, a dyestuif having similar properties is obtained.

We claim: 1. The phthalocyanine dyestuff of the formula Ho3s)..

MePc: Y-X-l ISO2Z) (H2NO2S)m wherein Pc represents phthalocyanine, Me represents a member selected from the group consisting of copper and nickel, Y represents a member selected from the group NH- consisting of NH, SO NH-lwer a1ky1ene-NH, SO2 NH ES SO2 NH 5 S'JaH SOsH I NHNH NH SO2-NH- SOPNH sour sour and 30 N N NH- 2 X represents a member selected from the group consistn ing of CO, SO and -CONH-, R represents SJHH a member selected from the group consisting of hydrogen NH and lower alkyl, R represents hydrogen or chlorine, Z represents a member selected from the group consisting sO2NH of -CH=CH and CH CH -Cl, n represents an integer from 1 to 3, m represents la number from 0 to 2, $0311 and p represents an integer from 1 to 2.

2. The dyestulf of the formula (3H3 nosey-{cum} so,NHQNH-co@Nsoiclrzorn-ci 3. The dyestufl? of the formula F Q H -0 I s0 -NH H OaS): L u 0-] 2 I 2 a NH-CONSO2OHzCH2Cl 2 4. The dyestuff of the formula OuPC-SOz-NH -SOsH i I (3H3 BIN-02S NH-C 0NSO2CHr-CH:C1

5. The dyestuif of the formula ([3113 (H OaS)zT :CuPc lTSO2NH-NHC ONS O2CHa-CH:C1

S OaH 6. The dyestutf of the formula $Hs NHO O-NSO2CHa-OHC1 l (HOaS)2 NiP0 SOrNHSOaH L .l E

References Cited by the Examiner UNITED STATES PATENTS 3,114,746 12/1963 Benz et a1 260-163 3,232,931 2/1966 Rothman 260242 WALTER A. MODANCE, Primary Exa'miner. JAMES A. PATTEN, Assistant Examiner. 

1. THE PHTHALOCYANNIE DYESTUFF OF THE FORMULA 